Novel transition-metal complexes and use thereof in transition-metal catalyzed reactions

Abstract

The invention relates to novel transition metal complexes of the formula (I) and (II), to processes for preparing these transition metal complexes, to intermediates for preparing them, and also to the use of the transition metal complexes as catalysts in organic reactions, particularly in metathesis reactions.

1 . Compounds of the formulae (I) and (II)  
       
         
           
           
               
               
           
         
       
       where 
 M is a transition metal of the 8th transition group of the Periodic Table,  
 X 1  and X 2  are the same or different and are each an anionic ligand,  
 R 1 , R 2 , R 3  and R 4  are the same or different and are each hydrogen, with the proviso that at least one radical R 1  to R 4  is different to hydrogen, or are each cyclic, straight-chain or branched alkyl radicals having from 1 to 50 carbon atoms or aryl radicals having from 6 to 30 carbon atoms, where at least one hydrogen atom in the radicals mentioned is optionally replaced by an alkyl group or a functional group, and R 1  and/or R 4  is also halogen, C 1 -C 4 -alkoxy, C 6 -C 10 -aryloxy, cyano, C 1 -C 4 -alkoxycarbonyl, C 6 -C 10 -aryloxycarbonyl or aliphatic or aromatic C 1 -C 10 -acyloxy, and/or  
 R 1  and R 2  or R 2  and R 3  or R 3  and R 4  or R 4  and R 5  are part of a cyclic system which consists of a carbon framework having from 3 to 20 carbon atoms, not including the carbon atoms in formula (I) and (II), where at least one hydrogen atom is optionally replaced by an alkyl group or a functional group, and/or at least one carbon atom of the cycle is optionally being replaced by a heteroatom from the group of S, P, O and N, and  
 R 5  is hydrogen or a cyclic, straight-chain or branched alkyl radical having from 1 to 20 carbon atoms or an aryl radical having from 6 to 20 carbon atoms, where at least one hydrogen atom in the radicals mentioned is optionally replaced by an alkyl group or a functional group, and  
 R 6  and R 7  are the same or different and are each cyclic, straight-chain or branched alkyl radicals having from 1 to 30 carbon atoms or are each aryl radicals having from 6 to 20 carbon atoms, where at least one hydrogen atom is optionally replaced by an alkyl group or a functional group.  
 
     
     
         2 . Compounds as claimed in  claim 1 , characterized in that 
 M is ruthenium or osmium,    X 1  and X 2  are the same or different and are each an anionic ligand from the group of halides, pseudohalides, hydroxides, alkoxides, carboxylates and sulphonates, the pseudohalides preferably being cyanide, thiocyanate, cyanate, isocyanate and isothiocyanate,    R 1 , R 2 , R 3  and R 4  are the same or different and are each hydrogen, with the proviso that at least one radical R 1  to R 4  is different to hydrogen, or are each cyclic, straight-chain or branched alkyl radicals having from 1 to 20 carbon atoms or aryl radicals having from 6 to 20 carbon atoms, where at least one hydrogen atom in the alkyl and aryl radicals mentioned is optionally replaced by a functional group, and R 1  and/or R 4  is halogen, C 1 -C 4 -alkoxy, C 6 -C 10 -aryloxy, cyano, C 1 -C 4 -alkoxycarbonyl, C 6 -C 10 -aryloxycarbonyl or aliphatic or aromatic C 1 -C 10 -acyloxy, or    R 1 , R 2  and R 3  are each hydrogen and R 4  is a cyclic, straight-chain or branched alkyl radical having from 1 to 20 carbon atoms or an aryl radical having from 6 to 20 carbon atoms, where at least one hydrogen atom in the radicals mentioned is optionally replaced by an alkyl group or a functional group, or is halogen, C 1 -C 4 -alkoxy, C 6 -C 10 -aryloxy, cyano, C 1 -C 4 -alkoxycarbonyl, C 6 -C 10 -aryloxycarbonyl or aliphatic or aromatic C 1 -C 10 -acyloxy, or    R 1  and R 4  are the same or different and are each hydrogen or an aryl radical having from 6 to 20 carbon atoms, where at least one hydrogen atom in the aryl radical is optionally replaced by an alkyl group or a functional group, or are each halogen, C 1 -C 4 -alkoxy, C 6 -C 10 -aryloxy, cyano, C 1 -C 4 -alkoxycarbonyl, C 6 -C 10 -aryloxycarbonyl or aliphatic or aromatic C 1 -C 10 -acyloxy and R 2  and R 3  are part of a cyclic aromatic system having from 4 to 14 carbon atoms, not including the carbon atoms in formulae (I) and (II) of  claim 1 , where at least one hydrogen atom is optionally replaced by an alkyl group or a functional group, or R 5  is a straight-chain or branched alkyl radical having 1 to 20 carbon atoms, and    R 6  and R 7  are the same or different and are each aryl radicals having from 6 to 14 carbon atoms, where at least one hydrogen atom is optionally replaced by an alkyl group or a functional group.    
     
     
         3 . Compounds as claimed in  claim 1 , characterized in that 
 M is ruthenium,    X 1  and X 2  are the same and are each an anionic ligand from the group of halides and pseudohalides, the pseudohalides preferably being cyanide, thiocyanate, cyanate and isocyanate,    R 1 , R 2 , R 3  and R 4  are the same or different and are each hydrogen, with the proviso that at least one radical R 1  to R 4  is different to hydrogen, or are each cyclic, straight-chain or branched alkyl radicals having from 1 to 10 carbon atoms or aryl radicals having from 6 to 14 carbon atoms, where at least one hydrogen atom in the alkyl or aryl radicals mentioned is optionally replaced by an alkyl group or a functional group, and R 1  and/or R 4  is halogen, C 1 -C 4 -alkoxy, C 6 -C 10 -aryloxy, cyano, C 1 -C 4 -alkoxycarbonyl, C 6 -C 10 -aryloxycarbonyl or aliphatic or aromatic C 1 -C 10 -acyloxy, or    R 1 , R 2  and R 3  are each hydrogen and R 4  is an aryl radical having from 6 to 14 carbon atoms, where at least one hydrogen atom in the aryl radical is optionally replaced by an alkyl group or a functional group, or is halogen, C 1 -C 4 -alkoxy, C 6 -C 10 -aryloxy, cyano, C 1 -C 4 -alkoxy-carbonyl, C 6 -C 10 -aryloxycarbonyl or aliphatic or aromatic C 1 -C 10 -acyloxy, or    R 1  is hydrogen or halogen, C 1 -C 4 -alkoxy, C 6 -C 10 -aryloxy, cyano, C 1 -C 4 -alkoxycarbonyl, C 6 -C 10 -aryloxycarbonyl or aliphatic or aromatic C 1 -C 10 -acyloxy and R 4  is hydrogen or an aryl radical having from 6 to 14 carbon atoms, where at least one hydrogen atom in the aryl radical is optionally replaced by an alkyl group or a functional group, or is halogen, C 1 -C 4 -alkoxy, C 6 -C 10 -aryloxy, cyano, C 1 -C 4 -alkoxycarbonyl, C 6 -C 10 -aryloxycarbonyl or aliphatic or aromatic C 1 -C 10 -acyloxy, and R 2  and R 3  are part of a cyclic aromatic system having from 4 to 8 carbon atoms, not including the carbon atoms in formula (I) of  claim 1 , where at least one hydrogen atom is optionally replaced by an alkyl group or a functional group, or    R 5  is a branched alkyl radical having from 3 to 8 carbon atoms, and    R 6  and R 7  are identical aryl radicals having from 6 to 10 carbon atoms, where at least one hydrogen atom is preferably replaced by an alkyl group or a functional group.    
     
     
         4 . A process for preparing compounds of the formulae (I) and (II) as claimed in at least one of  claims 1  to  3 , by exchanging the phosphine ligand PZ 3  in compounds of the formula (VI)  
       
         
           
           
               
               
           
         
       
       where 
 L is  
                     
 and  
 R 6  and R 7  are each as defined in  claims 1  to  3  and  
 M, X 1  and X 2  are each as defined in  claims 1  to  3  by ligands of the formula (VII)  
                     
 where R 1  to R 5  are each as defined in  claims 1  to  3 .  
 
     
     
         5 . The process as claimed in  claim 4 , characterized in that the reaction takes place in the presence of compounds which are capable of scavenging phosphines.  
     
     
         6 . Compounds of the formula (VII)  
       
         
           
           
               
               
           
         
       
       where 
 R 1 , R 2 , R 3  and R 4  are the same or different and are each hydrogen, with the proviso that at least one radical R 1  to R 4  is different to hydrogen, or are each cyclic, straight-chain or branched alkyl radicals having from 1 to 50 carbon atoms or aryl radicals having from 6 to 30 carbon atoms, where at least one hydrogen atom in the radicals mentioned is optionally replaced by an alkyl group or a functional group, and R 1  and/or R 4  is also halogen, C 1 -C 4 -alkoxy, C 6 -C 10 -aryloxy, cyano, C 1 -C 4 -alkoxycarbonyl, C 6 -C 10 -aryloxycarbonyl or aliphatic or aromatic C 1 -C 10 -acyloxy, and/or  
 R 1  and R 2  or R 2  and R 3  or R 3  and R 4  or R 4  and R 5  are part of a cyclic system which consists of a carbon framework having from 3 to 20 carbon atoms, not including the carbon atoms in formula (I) and (II), where at least one hydrogen atom is optionally replaced by an alkyl group or a functional group, and/or at least one carbon atom of the cycle is optionally being replaced by a heteroatom from the group of S, P, O and N, and  
 R 5  is hydrogen or a cyclic, straight-chain or branched alkyl radical having from 1 to 20 carbon atoms or an aryl radical having from 6 to 20 carbon atoms, where at least one hydrogen atom in the radicals mentioned is optionally replaced by an alkyl group or a functional group.  
 
     
     
         7 . Compounds of the formula (VII) as claimed in  claim 6  where 
 R 1 , R 2 , R 3  and R 4  are the same or different and are each hydrogen, with the proviso that at least one radical R 1  to R 4  is different to hydrogen, or are each cyclic, straight-chain or branched alkyl radicals having from 1 to 20 carbon atoms or aryl radicals having from 6 to 20 carbon atoms, where at least one hydrogen atom in the alkyl and aryl radicals mentioned is optionally replaced by a functional group, and R 1  and/or R 4  is halogen, C 1 -C 4 -alkoxy, C 6 -C 10 -aryloxy, cyano, C 1 -C 4 -alkoxycarbonyl, C 6 -C 10 -aryloxycarbonyl or aliphatic or aromatic C 1 -C 10 -acyloxy, or  
 R 1 , R 2  and R 3  are each hydrogen and R 4  is a cyclic, straight-chain or branched alkyl radical having from 1 to 20 carbon atoms or an aryl radical having from 6 to 20 carbon atoms, where at least one hydrogen atom in the radicals mentioned is optionally replaced by an alkyl group or a functional group, or is halogen, C 1 -C 4 -alkoxy, C 6 -C 1 -aryloxy, cyano, C 1 -C 4 -alkoxycarbonyl, C 6 -C 10 -aryloxycarbonyl or aliphatic or aromatic C 1 -C 10 -acyloxy, or  
 R 1  and R 4  are the same or different and are each hydrogen or an aryl radical having from 6 to 20 carbon atoms, where at least one hydrogen atom in the aryl radical is optionally replaced by an alkyl group or a functional group, or are each halogen, C 1 -C 4 -alkoxy, C 6 -C 10 -aryloxy, cyano, C 1 -C 4 -alkoxycarbonyl, C 6 -C 10 -aryloxycarbonyl or aliphatic or aromatic C 1 -C 10 -acyloxy and R 2  and R 3  are part of a cyclic aromatic system having from 4 to 14 carbon atoms, not including the carbon atoms in formulae (I) and (II) of  claim 1 , where at least one hydrogen atom is optionally replaced by an alkyl group or a functional group, or  
 R 5  is a straight-chain or branched alkyl radical having 1 to 20 carbon atoms.  
 
     
     
         8 . A process for preparing compounds of the formula (VII) as claimed in claims  6  and  7 , by converting compounds of the formula (XI)  
       
         
           
           
               
               
           
         
       
       in a Wittig reaction.  
     
     
         8 . The use of the compounds of the formula (I) and (II) as claimed in  claims 1  to  3  as catalysts.  
     
     
         9 . The use of the compounds of the formula (I) and (II) as claimed in  claims 1  to  3  as catalysts in a metathesis reaction.  
     
     
         10 . The use of the compounds of the formula (VII) as claimed in claims  6  and  7  as ligands for preparing transition metal complexes.